CN104200952B - A kind of flexible ferrite rubber magnet of Halogen oil-resistant high-temperature and preparation method thereof - Google Patents
A kind of flexible ferrite rubber magnet of Halogen oil-resistant high-temperature and preparation method thereof Download PDFInfo
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- CN104200952B CN104200952B CN201410381899.6A CN201410381899A CN104200952B CN 104200952 B CN104200952 B CN 104200952B CN 201410381899 A CN201410381899 A CN 201410381899A CN 104200952 B CN104200952 B CN 104200952B
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Abstract
The invention discloses a kind of formula of flexible ferrite rubber magnet of Halogen oil-resistant high-temperature and its preparation technology.The flexible ferrite rubber magnet of the Halogen oil-resistant high-temperature, including following parts by weight：Ferromagnetic oxide powder：85 93 parts, super heated rubber：5 12 parts, processing aid：15 parts, vulcanizing agent：0.5 3 parts.The present inventor passes through the reasonable cooperation to super heated rubber system and ferromagnetic oxide powder, technique is optimized, introduction laminates process and significantly improves magnetic characteristic, allow made rubber magnet that still there is preferable magnetic characteristic and circumnutating property at high temperature, meet resistant to elevated temperatures requirement, according to the difference from rubbery system, maximum operation (service) temperature is up to 120 170 DEG C, it compensate for the deficiency that existing rubber magnet temperature tolerance only up to be resistance to 100 DEG C, the application of rubber magnet is expanded, there will be wide market prospects especially for automobile industry.
Description
Technical field
The invention belongs to bonded magnetic material field, in particular it relates to a kind of flexible ferrite of Halogen oil-resistant high-temperature
Rubber magnet and preparation method thereof, is mainly used in micro machine and fan motor.
Background technology
Flexible ferrite rubber magnet since the advent of the world, is widely used to household electrical appliances, office, computer, automobile and automation
Etc. industry, various small and special electric machines, radiator fan and magnetic attracting device are manufactured, compared with ferrite sintered body, because using rubber processing work
Skill is produced, and power consumption of polymer processing is low, and continuous batch production can be achieved, and production efficiency is high, product can free bend without ftractureing, size shape
The shape free degree is big, can arbitrarily cut, without die sinking, saves client development expense, and size can accomplish smaller, and precision is higher, thick
Degree minimum can reach 0.5mm, be easily formed radial anisotropy product and be easy to radiation multipolar to magnetize, and client uses very square
Just the advantages of, the market of major part sintered magnet has been instead of.But existing flexible ferrite rubber magnet is main viscous
It is that CPE or NBR, CPE contain halogen to connect agent, and maximum operation (service) temperature only has 85 DEG C, can be produced when being burnt because of halogen containing material big
The smog of amount and poisonous corrosive hydrogen halides gas, cause secondary hazards, so cry of the existing electronic product industry to Halogen
More and more higher, many producers all start to implement product the management and control of Halogen；NBR is free of halogen, but its maximum operation (service) temperature is only
There are 100 DEG C, compared with the maximum operation (service) temperature of 400 DEG C of sintered magnet, temperature in use is substantially reduced, and is requiring the garage of high temperature
The industries such as industry are using being restricted.Although in patent ZL200610089260.6, being related to high temperature ferrite rubber
Invention, but its rubber used is fluorubber, or organosilicon and NBR paralled system, fluorubber belongs to halogen rubber, no
Meet the requirement of Halogen, and process relatively difficult, it is expensive；Organosilicon is siliceous organic due to that can volatilize some at high temperature
Thing, these organic matters can be attached on the brush of motor, and influence is produced on the electric conductivity of brush, general in micro machine motor industry
The compound using organosilicon and its correlation is not allowed, so the magnet of both rubbery systems is also unable to reach batch production
For the purpose in the micro machine motor of automobile industry.
The content of the invention
The purpose of the present invention is exactly to solve the not enough shortcoming of existing rubber magnet temperature tolerance to have high performance-price ratio there is provided one kind
The ferrite halide-free rubber magnet of oil-resistant high-temperature and preparation method thereof.
One of goal of the invention of the present invention is realized by following proposal：
A kind of flexible ferrite rubber magnet of Halogen oil-resistant high-temperature, including following parts by weight：
Wherein, the super heated rubber includes：Ethylene-acrylate rubber, ethylene vinyl acetate rubber, acrylate rubber
Glue, hydrogenated nitrile-butadiene rubber one of which or more than one blend rubber systems.
Wherein, the super heated rubber includes：Ethylene-acrylate rubber, ethylene vinyl acetate rubber, acrylate rubber
The blend rubber system of glue, hydrogenated nitrile-butadiene rubber wherein one or more and nitrile rubber (NBR).
According to the difference from rubbery system, its temperature tolerance is 120 DEG C to 170 DEG C, it is possible to provide the rubber of different heatproof purposes
Glue magnet.
Wherein, the ferromagnetic oxide powder includes：Anisotropy strontium ferrite, isotropism strontium ferrite, barium ferrite.
Rubber chemicals used in the present invention include lubricant, age resistor, plasticizer and heat-resistant agent etc., wherein lubricant bag
Include zinc stearate, stearic acid, fatty acid ester, paraffin etc.；Age resistor includes substituted diphenylamine, p-phenylenediamine class (Antiox
445), Mercaptophenylimidazole (MB), 2,2,4- trimethyl -1,2 dihyaroquinoline condensates, microwax, etc.；Plasticizer includes
Trioctyl trimellitate (TOTM) (TOTM), adipic acid two (Butoxyethoxy second) ester (TP95), etc.；Heat-resistant agent includes magnesia, first
Base zinc acrylate resin, magnesinm methacrylate etc., heat-resistant agent especially have obvious effect in the paralled system of NBR and other rubber
Really.
Vulcanizing agent used in the present invention includes peroxide and amine curing agents.Including tert-butyl cumene peroxide
Compound, 2,5- dimethyl -2,5- double (benzoyl peroxide) hexane, cumyl peroxide (DCP), Isosorbide-5-Nitraes-bis- (tert-butyl peroxies
Base) diisopropylbenzene (DIPB), hexa-methylene carbaminate (No. 1 vulcanizing agent), ethylene-diamine carbamate etc..
The particle diameter of the ferromagnetic oxide powder is in 1.0-2.0um.
Another goal of the invention of the present invention is：A kind of preparation of the flexible ferrite rubber magnet of Halogen oil-resistant high-temperature
Method, it is characterized in that：Comprise the following steps：
Kneaded uniformly Step 1: will in proportion be put into after magnetic, rubber, auxiliary agent precise in banbury,
Vulcanizing agent mixing is added Step 2: the raw material after mixing is cooled to after less than 100 DEG C uniformly,
Step 3: then banburying material to be pressed into 1.5-2.5mm thin slice on two roll calender, 3-8 plate sheets are pressed
Prolong machine and be laminated to 2mm thickness for continuous 3-8 times, carry out mechanical orientation to improve magnetic characteristic.
Step 4: the piece after calendering is vulcanized by continuous vulcanization stove, the excellent flexible iron of oil resistant temperature tolerance is obtained
Oxysome rubber magnet.
Wherein, the temperature of banburying is 130~150 DEG C.
Wherein, the technique that the mechanical orientation improves magnetic characteristic is orientated by 3-8 platform calenders continuous calendering.
Wherein, the sulfuration process is microwave vulcanization or hot-air cure or drum-type vulcanization or infra-red vulcanization or flat board sulphur
Change.
Its manufacturing process is will to put into banbury to knead uniformly to 130-150 after magnetic, rubber, auxiliary agent precise
DEG C, less than 100 DEG C are then cooled to, vulcanizing agent mixing is added uniformly, is then pressed into banburying material on two roll calender
The thin slice of 1.5-2.5mm thickness, 3-8 plate sheets are laminated for continuous 3-8 times with calender and carry out mechanical orientation to improve magnetic characteristic,
And the thickness 2mm needed, eventually pass continuous vulcanization stove and vulcanized, obtain the excellent flexible ferrite of oil resistant temperature tolerance
Rubber magnet, finally by the sheet material after vulcanization cut into the size of client's needs.Continuous machine is laminated by many calenders
Tool is orientated, and its magnetic characteristic Br can improve 5-10%, and tensile strength and circumnutating property will be improved significantly.
Manufacturing process is as follows：
Banburying → slice → laminates → continuous vulcanization → and cut
Of the invention temperature tolerance is improved significantly compared with existing flexible rubber magnet, according to different bonding agent bodies
System can obtain different temperature resistant rubber magnets, and cost also can be accordingly adjusted.
Embodiment
The Chinese control of general profession symbol, term and the unit occurred in the present invention is as follows：
NBR is nitrile rubber；EVM is ethylene vinyl acetate rubber；AEM is ethylene-acrylate rubber；ACM is propylene
Acid esters rubber；HNBR is hydrogenated nitrile-butadiene rubber.
TP95 is plasticizer adipic acid two (Butoxyethoxy second) ester；MB is age resistor Mercaptophenylimidazole；Aniox
445 be age resistor p-phenylenediamine class；DCP is vulcanizing agent cumyl peroxide；No. 1 vulcanizing agent is hexa-methylene carbamic acid
Salt.
Br is residual magnetic flux density, abbreviation remanent magnetism；Hcb is coercivity；Hcj is HCJ；(BH) max is maximum
Magnetic energy product；Shore D are shore hardness D types；
GS：It is Br unit, Gaussian system (CGS), Gauss.
Oe：It is Hcb and Hcj unit, Gaussian system (CGS), oersted.
MGOe：It is (BH) max unit, Gaussian system (CGS), million high oersteds.
Embodiment 1
It is formulated NO1：
NBR：500g
HNBR：500g
Strontium ferrite magnetic powder：10kg
Zinc stearate：10g
TP95：50g
Magnesia：50g
MB：20g
DCP：20g
Material in the above-mentioned formula of precise, adds in banbury and kneads uniformly to 145 DEG C, be then cooled to 100 DEG C
Hereinafter, add vulcanizing agent mixing uniform, then banburying material is pressed into the thin slice of 2mm thickness on two roll calender, by several pieces
Thin slice is laminated with calender continuous several times carries out mechanical orientation to improve magnetic characteristic, and the thickness needed, and the present embodiment is
Thin slice, is then put into continuous vulcanization stove and vulcanizes by 2mm.Magnetic film after vulcanization is measured into magnetic characteristic and high temperature ageing examination is done
Test, the results are shown in Table 1-5：
Embodiment 2
It is formulated NO2：
NBR：300g
HNBR：680g
Strontium ferrite magnetic powder：10kg
Zinc stearate：10g
TP95：60g
Magnesia：30g
MB：20g
DCP：20g
Material in the above-mentioned formula of precise, adds in banbury and kneads uniformly to 140 DEG C, be then cooled to 100 DEG C
Hereinafter, add vulcanizing agent mixing uniform, then banburying material is pressed into the thin slice of 2mm thickness on two roll calender, by several pieces
Thin slice is laminated with calender continuous several times carries out mechanical orientation to improve magnetic characteristic, and the thickness needed, and the present embodiment is
Thin slice, is then put into continuous vulcanization stove and vulcanizes by 2mm.Magnetic film after vulcanization is measured into magnetic characteristic and high temperature ageing examination is done
Test, the results are shown in Table 1-5：
Embodiment 3
It is formulated NO3：
HNBR：980g
Strontium ferrite magnetic powder：10kg
Zinc stearate：10g
TP95：80g
MB：20g
DCP：20g
Material in the above-mentioned formula of precise, adds in banbury and kneads uniformly to 150 DEG C, be then cooled to 100 DEG C
Hereinafter, add vulcanizing agent mixing uniform, then banburying material is pressed into the thin slice of 2mm thickness on two roll calender, by several pieces
Thin slice is laminated with calender continuous several times carries out mechanical orientation to improve magnetic characteristic, and the thickness needed, and the present embodiment is
Thin slice, is then put into continuous vulcanization stove and vulcanizes by 2mm.Magnetic film after vulcanization is measured into magnetic characteristic and high temperature ageing examination is done
Test, the results are shown in Table 1-5：
Embodiment 4
It is formulated NO4：
HNBR：490g
EVM:490g
Strontium ferrite magnetic powder：10kg
Stearic acid：10g
TP95：50g
MB：20g
DCP：20g
Material in the above-mentioned formula of precise, adds in banbury and kneads uniformly to 135 DEG C, be then cooled to 100 DEG C
Hereinafter, add vulcanizing agent mixing uniform, then banburying material is pressed into the thin slice of 2mm thickness on two roll calender, by several pieces
Thin slice is laminated with calender continuous several times carries out mechanical orientation to improve magnetic characteristic, and the thickness needed, and the present embodiment is
Thin slice, is then put into continuous vulcanization stove and vulcanizes by 2mm.Magnetic film after vulcanization is measured into magnetic characteristic and high temperature ageing examination is done
Test, the results are shown in Table 1-5：
Embodiment 5
It is formulated NO5：
AEM：1000g
Strontium ferrite magnetic powder：10kg
Stearic acid：15g
TP95：50g
Antiox 445：20g
No. 1 vulcanizing agent：20g
Material in the above-mentioned formula of precise, adds in banbury and kneads uniformly to 145 DEG C, be then cooled to 100 DEG C
Hereinafter, add vulcanizing agent mixing uniform, then banburying material is pressed into the thin slice of 2mm thickness on two roll calender, by several pieces
Thin slice is laminated with calender continuous several times carries out mechanical orientation to improve magnetic characteristic, and the thickness needed, and the present embodiment is
Thin slice, is then put into continuous vulcanization stove and vulcanizes by 2mm.Magnetic film after vulcanization is measured into magnetic characteristic and high temperature ageing examination is done
Test, the results are shown in Table 1-5：
Embodiment 6
It is formulated NO6：
ACM：1030g
Strontium ferrite magnetic powder：10kg
Stearic acid：15g
TP95：50g
Antiox 445：20g
No. 1 vulcanizing agent：20g
Material in the above-mentioned formula of precise, adds in banbury and kneads uniformly to 138 DEG C, be then cooled to 100 DEG C
Hereinafter, add vulcanizing agent mixing uniform, then banburying material is pressed into the thin slice of 2mm thickness on two roll calender, by several pieces
Thin slice is laminated with calender continuous several times carries out mechanical orientation to improve magnetic characteristic, and the thickness needed, and the present embodiment is
Thin slice, is then put into continuous vulcanization stove and vulcanizes by 2mm.Magnetic film after vulcanization is measured into magnetic characteristic and high temperature ageing examination is done
Test, the results are shown in Table 1-5：
Table 1：The magnetic characteristic and physical property of different bonding agent system magnet
The magnetic characteristic that NO1~NO6 is formulated in embodiment is substantially suitable with contrast groups, and ACM makees caking agent formula because of its intensity
It is poor, it is necessary to more bonding agents, so Br is more relatively low, circumnutating property is also more slightly worse, other several groups of hardness and circumnutating property with it is right
It is quite more even better than organizing, existing NBR magnets can be replaced to be used in micro machine motor completely.
Table 2：The circumnutating property of various caking agent series under different temperatures aging condition
The test of circumnutating property is to bend magnetic adhesive tape on the axle of interval difference 2mm different-diameter, observes its surface, remembers
The maximum gauge of crackle does not occur for record surface.Such as Φ 18mm represent magnetic adhesive tape bending OK on Φ 18mm axle, but bend
Just there is crackle generation on Φ 20mm axle.For micro machine motor magnetic rubber, needed when being used due to rubber magnet curved
Qu Chengyuan is used, so magnet must have certain circumnutating property.The change of circumnutating property is bigger, illustrates that magnetic adhesive tape aging is more serious.It is right
In the magnetic glue of 2mm thickness, the requirement of circumnutating property is usually at least Φ 22OK.
NO1~NO6 formulas are all well more many than contrast groups in embodiment, and the contrast groups using NBR as bonding agent are bent at 120 DEG C
Substantially it is deteriorated around property, it is impossible to use.NO1 formulas can be with resistance to 120 DEG C of high temperature ageing, and NO2, NO3 and NO6 formula can be with resistance to 140
DEG C high temperature ageing, NO4, NO5 can be with resistance to 160 DEG C of high temperature ageings.
Table 3：The firmness change (Shore D) of various caking agent series under different temperatures aging condition
Firmness change of NO1~NO6 formulas after high temperature ageing is also more much smaller than contrast groups in embodiment, and NO4 and NO5 match somebody with somebody
Side's hardness after 160 DEG C of agings just increases 12-13 degree, illustrates the formula system of embodiment more resistant to high temperature ageing.
Table 4：The influence (%) of the tensile strain rate of various caking agent series under different temperatures aging condition
The change of length after high temperature of NO1~NO6 formulas is smaller than contrast groups in embodiment, and length change is bigger, magnetic adhesive tape
Load easier loosening after micro machine motor, can seriously make motor out of service.And the formula system of embodiment, especially
Make the formula length change very little of bonding agent with HNBR and AEM respectively, illustrate it more resistant to high temperature.
Table 5：The influence (%) of the flux change rate of various caking agent series under different temperatures aging condition
The requirement rubber magnet of general micro machine motor producer is less than using the rate of change of rear magnetic flux at a certain temperature
5%, as can be seen from Table 5, the formula of embodiment and the flux change of contrast groups are all smaller, and temperature is higher, and flux change can be slightly
It is big, but 5% is both less than in addition to contrast groups.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should manage
Solution, technical scheme can be modified or equivalent substitution, without departing from technical solution of the present invention essence and
Scope.
Claims (6)
1. a kind of flexible ferrite rubber magnet of Halogen oil-resistant high-temperature, it is characterised in that：By the component group of following parts by weight
Into：
The super heated rubber is ethylene vinyl acetate rubber, ACM, hydrogenated nitrile-butadiene rubber one of which or one
Plant above blend rubber system；Or the super heated rubber is ethylene vinyl acetate rubber, ACM, hydrogenated butyronitrile
Rubber wherein one or more and the blend rubber system of nitrile rubber (NBR)；
The ferromagnetic oxide powder is isotropism strontium ferrite；
The flexible ferrite rubber magnet is used in micro machine motor.
2. according to the flexible ferrite rubber magnet of claim 1 Halogen oil-resistant high-temperature, it is characterised in that：The ferrite magnetic
The particle diameter of powder is in 1.0-2.0um.
3. a kind of system of the flexible ferrite rubber magnet of Halogen oil-resistant high-temperature as described in claim 1 to 2 any one
Preparation Method, it is characterized in that：Comprise the following steps：
Kneaded uniformly Step 1: will in proportion be put into after magnetic, rubber, auxiliary agent precise in banbury,
Vulcanizing agent mixing is added Step 2: the raw material after mixing is cooled to after less than 100 DEG C uniformly,
Step 3: then banburying material to be pressed into 1.5-2.5mm thin slice on two roll calender, by 3-8 plate sheet calenders
Be laminated to 2mm thickness continuous 3-8 time, progress mechanical orientation to improve magnetic characteristic,
Step 4: the piece after calendering is vulcanized by continuous vulcanization stove, the excellent flexible ferrite of oil resistant temperature tolerance is obtained
Rubber magnet.
4. the preparation method of the flexible ferrite rubber magnet of a Halogen oil-resistant high-temperature according to claim 3, its
It is characterised by：The temperature of banburying is at 130~150 DEG C.
5. the preparation method of the flexible ferrite rubber magnet of a Halogen oil-resistant high-temperature according to claim 3, its
It is characterised by：The technique that the mechanical orientation improves magnetic characteristic is orientated by 3-8 platform calenders continuous calendering.
6. the preparation method of the flexible ferrite rubber magnet of a Halogen oil-resistant high-temperature according to claim 3, its
It is characterised by：The sulfuration process is microwave vulcanization or hot-air cure or drum-type vulcanization or infra-red vulcanization or compression molding.
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| JP6682113B2 (en) * | 2015-11-18 | 2020-04-15 | 内山工業株式会社 | Magnetic rubber composition, magnetic rubber molded product, magnetic encoder, and methods for producing the same |
| CN107967975A (en) * | 2017-12-13 | 2018-04-27 | 江西伟普科技有限公司 | A kind of preparation method of the corrosion resistant environment-friendly type injection molding adhesion magnetic material of high specific gravity |
| CN109294018A (en) * | 2018-10-30 | 2019-02-01 | 浙江宏利汽车零部件有限公司 | A kind of nitrile rubber of the resistance to ozone-type of oil resistant |
| CN109360704A (en) * | 2018-11-07 | 2019-02-19 | 吴克鸽 | A kind of silicon rubber diskette and its manufacturing method |
| CN111048299B (en) * | 2020-01-07 | 2022-06-07 | 广州金南磁性材料有限公司 | Bonded magnet and preparation method thereof |
| CN112280096A (en) * | 2020-10-12 | 2021-01-29 | 广州金南磁性材料有限公司 | Regenerated rubber magnet and preparation method and application thereof |
| CN112563011A (en) * | 2020-11-10 | 2021-03-26 | 广州金南磁性材料有限公司 | Flexible neodymium-iron-boron magnet and preparation method and application thereof |
| CN113150472B (en) * | 2021-05-07 | 2022-03-15 | 青岛睿智森油封有限公司 | Octavinyl-cage type silsesquioxane modified fluororubber |
| CN114974865A (en) * | 2022-05-07 | 2022-08-30 | 广州金南磁性材料有限公司 | Rubber magnetic material and preparation method and application thereof |
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